water and wastewater analysis following catastrophic - nemc
TRANSCRIPT
Water and Wastewater Analysis
Following Catastrophic Events
Matthew L. Magnuson & Hiba S. Ernst
US Environmental Protection Agency/Office of Research and Development
National Homeland Security Research Center/Water Infrastructure Protection Division
National Environmental Monitoring Conference
San Antonio, TX, August 5-8, 2013
Presentation Overview
• Lab analysis during catastrophic events - Is there a
difference?
• What is being done?
– Lab Networks
– Pre-selected and verified methods
– Biotoxin research projects
– Chemistry research projects
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NHSRC Mission
To conduct research and develop scientific products that
improve the capability of the Agency to carry out its homeland
security responsibilities
ADVANCING
OUR NATION’S
SECURITY
THROUGH
SCIENCE
EPA Homeland Security Roles
• Protecting water and wastewater infrastructure
• Indoor and outdoor clean-up following attack or natural disaster
can use millions of gallons of water
can result in even more contaminated wastewater
• Development of a nationwide laboratory network
• Reducing vulnerability of chemical & hazardous materials
• Cyber security
Many homeland security practices may also benefit
day to day operation. For example, emerging
analytical techniques useful for water emergencies
and/or clean-up after contamination might also be
useful for monitoring water quality.
Multi Use
Homeland Security
“Normal” Environmental
Operations
Cross Agency
NHSRC Research Projects
Water Security & Sustainability
6
7
Water Security Threats
• Multiple points of access
over thousands of miles of
pipe
• Vulnerable to insider,
physical, and cyber threats
• Vulnerable to intentional or
accidental contamination
(e.g., injection at hydrant or
cross-connection)
• Contamination might not
be detected until people
are sick or in the hospital
• Intelligence information on
adversary capabilities
Water Distribution Networks
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• Wide area contamination release could affect water sources.
• Water can become contaminated not only from the initial
release, but also as a result of decontamination activities.
• Millions of gallons of water may be used for decon.
• Contaminated water may enter the storm or wastewater
collection system, impacting the wastewater treatment plant
and receiving waters.
Why Waste Water?
CBR Decontamination and Consequence
Management Paradigm
Spread of
Contamination
Waste
Management
Decon
Method
Contamination
Characteristics
• Dispersion
• Resuspension
• Tracking
• Efficacy
• Engineering
• Persistence
• Chemical
• Physical
• Pre-decon
• Post-decon
• Treatment/
Handling
Analysis is key
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Possible Numbers of Samples
from an Incident
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Potential approaches • High throughput sampling techniques and laboratory
analysis techniques, including automated or rapid
method capabilities
• Methods which can be applied to multiple labs by
Environmental Response Laboratory Network
(ERLN) and Water Laboratory Alliance
Meeting Lab Throughput
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SAM 2012 Published: July 2012
Chemical Methods
142 analytes
5 matrices
Pathogen Methods
31 analytes
4 matrices
Radiochemical Methods
25 analytes
6 matrices
Biotoxin Methods
18 analytes
5 matrices
www.epa.gov/sam
Selected Analytical Methods (SAM)
Laboratory Method
Development
• Methods aim to have data quality objectives (DQOs) fit
for their intended use by
– EPA/Water Security Division through the Water
Laboratory Alliance
– EPA/Office of Emergency Management through the
Environmental Response Laboratory Network
• Availability of Method and Study Reports
– Availability announced on website, and we also
maintain a list of stakeholders who are specifically
informed
– Register at http://www.epa.gov/nhsrc
NHSRC Research Products
• Results presented many other ways—stakeholder meetings, symposia,
workshops, etc.
• Products and research plans receive rigorous quality reviews
Most scientists regarded the new streamlined
peer-review process as ‘quite an improvement.’
Method Development in Water Matrices
(Biotoxins and Chem)
• Protein
– Abrin, Ricin, Botulinum neurotoxin (A, B, E, F), Shiga
1 & 2, Staphylococcal Enterotoxin (A, B, C)
• Small molecule
– Aflatoxin B1, α-Amanitin, anatoxin-a, brevetoxin B,
α-Conotoxin, Cylindrospermopsin,
Diacetoxyscirpenol, microcystins (LA, LR, LW, RR,
YR), picrotoxin, saxitoxins, T2 mycotoxin,
tetrodotoxin
Method Development for
Biotoxins
• Analytical techniques
– Antibody-based detection schemes
• Enzyme Linked Immunosorbant Assay (ELISA)
• Lateral flow devices
• Various antibody-capture-release detectors
(fluorescence, electrochemiluminescence, etc.)
– Instrumental analysis
• Liquid chromatography-mass spectrometry
• Gas chromatography-mass spectrometry
• others
Detection of Biotoxins
Meeting Throughput Requirements
Multi-tier analysis approach
• Environmental restoration hopefully is effective, so while there are
many samples, fewer will be positive after initial decontamination
activities
• Samples initially subjected to higher throughput screening methods
• Followed by analysis of selected samples with lower throughput, but
more definitive, techniques
• Application approach of techniques listed will appear in future version
of SAM (e.g. see techniques of ricin in table below)
Biotoxin Detection Projects
Centers for Disease Control and Prevention
• Quantitation of biotoxins via methods adapted from clinical
matrices such as urine
• LC/MS/MS methods, as used in chemical laboratory response
network (LRN) for clinical samples
– Adaptation to drinking water matrices
– Stability, extraction, chromatography, MS tuning
– High throughput, small samples, automation, IT
• Enzyme Linked Immunosorbant Assay (ELISA) for Botulinum
toxin in clinical samples and food adapted to water
• Endopep-MS (enzymatic activity) method adapted to water
samples
• Ability of the ultrafiltration (UF) technique to concentrate
botulinum toxin in water samples
• 100-1000 samples/day
• Analytes
– Alpha amanitin
– TETS
– Biomarkers for ricin and abrin
• Stable Isotopic Internal Standards
Native
Labeled
ISTD
NHHN
NH
HN
NH HN
HN
O
O
O
O
O
O
O
OS
O
H2N
O
N
HN
OH
Exact Mass: 918.35
HO
OH
HO
4,5-dihydroxyisoleucine4-hydroxyprolin
e
asparagine
glycine
isoleucine
glycine
4-hydroxytryptophan
cysteine
-amanitin
Features of Adapted Methods
Method Development
for Chemicals
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• Use methods as written, for lab familiarity
• Understand performance, demonstrate all steps
including QC
• Examples
Semi-volatiles (e.g. pesticides)
CWA transformation products
Metals
Verification of Chemicals
in Existing Method
BuChE Magnetic Bead
1) Conjugation of
antibody to beads
2) Binding of
antibody to
BuChE
Antibody Peptides
4) LC/MS/MS Analysis
3) Protein
digestion
3) Expose
to water
Immunomagnetic Scavenging and
LC/MS Detection of VX in Water
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IMSc LC-MS/MS Method
for Detection of VX in Water
• Method sensitivity down to the ppt level
– Calculated method detection limit = 5.6 ng/L
– Minimum reportable level = 25 ng/L
– Small sample size (100 mL)
• Can be used to analyze up to 500 samples per day
• Low concentrations of VX can be detected in
preserved tap water 91 days after spiking
– Suggests applicability of this method for
determining water contamination with VX and
verifying environmental remediation
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Wastewater Treatment Process
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Analysis for System Studies
Degradation of contaminants by activated sludge
Example contaminants:
EMPA (ethyl methyl phosphonic acid) : Environmental
and decon product of VX, determined by LC/MS/MS
Malathion: Simulant for VX, determined by GC/MS
Evaluated total suspended solid concentration and
contact time
Conclusions:
• If nitrifiers are active, they might degrade the analyte of
concern (less than 25 percent)
• EMPA, malathion, and similarly sorbed and biodegraded
compounds may pass through an activated sludge
wastewater treatment plant largely unchanged
Future Directions
• Extension to “All-hazard” catastrophes –natural
disasters, industrial accidents, etc
• Analysis approaches for other matrices
• Additional biotoxins and chemicals
• Refinement of existing methods
• Application-focused studies (decontamination,
system operations, etc.)
• Enhanced collaborations
– Federal (e.g. recent EPA, DHS, and DOD agreement)
– Other: maybe YOU?!
Acknowledgements
• Centers for Disease Control and Prevention
– Rudy Johnson, Ph.D.
– Jennifer Links, Ph.D.
– Stephen Morse, Ph.D.
– CT method development group
• Food Safety Inspection Service
– Mark Campbell, Ph.D.
– Marcus Head, Ph.D.
– Jim Jones, Ph.D.
– Anne Hurley, DVM, MPH
• US Air Force Institute of Technology
– Maj. LeeAnn Racz, Ph.D.
– Lt. Allen Janeckso, M.S.
– Maj. Edward Walters, M.S.
• Naval Surface Warfare Center
– Elaine Strauss, Ph.D.
– Wynn Vo
– Andrew Slaterbeck, Ph.D.
– Bradford Gutting, Ph.D.
• Environmental Protection Agency
– Michelle Burgess, Ph.D., EPA
– Sanjiv Shah, Ph.D., NHSRC
– Gene Rice, Ph.D., NHSRC
– Hiba Ernst, Ph.D., NHSRC
– Alan Lindquist, Ph.D., NHSRC
– Frank Schaefer, Ph.D., NHSRC
– Vince Gallardo
– Tonya, Nichols, Ph.D., NHSRC
Acknowledgements
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Co-authors/Collaborators: Romy Campisano
Erin Silvestri
Stuart Willison
U.S. EPA, National Homeland Security Research Center
Website: www.epa.gov/sam
SAM 2012 Published: July 2012
DISCLAIMER: The U.S. EPA through its Office of Research and
Development partially funded the research described in this
presentation. It has been reviewed by the Agency but does not
necessarily reflect the Agency’s views. No official endorsement
should be inferred. EPA does not endorse the purchase or sale
of any commercial products or services.
Matthew Magnuson, Ph.D.
Acting Associate Director/Chemist
Water Infrastructure Protection Division
[email protected]; 513-569-7321